Cycloaliphatic sulfite esters have found wide acceptance as pesticides, particularly as miticides, and as plasticizers. A particularly valuable class of intermediates for the production of such ester compounds are phenoxycycloalkanols. Thus, Covey et al., in U.S. Pat. No. 3,272,854 show the use of phenoxycycloalkanols as intermediates in the production of cycloaliphatic sulfite esters.
Moreover, U.S. Pat. No. 3,272,854 further discloses a method of producing phenoxycycloalkanols, which method comprises reacting p-tert-butylphenol with cyclohexene oxide in the presence of 1 to 1.5% by weight, based on the weight of the p-tert-butylphenol, of sodium hydroxide. However, a difficulty associated with such sodium hydroxide catalyzed process is that a relatively large concentration of sodium hydroxide is required. This requirement imposes an economic penalty as well as necessitates neutralization of the product of the reaction with acid and removal of the water of neutralization formed thereby. Moreover, as is illustrated in the Examples below, the use of sodi:ar hydroxide results in the production of comparatively large amounts of undesirable by-products.
Gentles, in U.S. Pat. No. 3,042,666 discloses a process for the manufacture of polyether derivatives comprising reacting polyhydroxylic compounds with alkylene oxides employing dimethylsulfoxide as a reaction medium and an alkaline catalyst, for example alkali metals and alkaline earth metals or hydroxides of such metals. This reaction is performed at a temperature between 50.degree. C. and 150.degree. C., preferably between 90.degree. C. and 120.degree. C.
Benoit, in U.S. Pat. No. 3,723,294, discloses a process for the copolymerization of an alcohol, preferably a monohydroxy aliphatic alcohol, and a mixture of alkene oxides containing propene oxide and pentene oxide. This process employs a catalyst which may be an alkali metal hydroxide or alkali metal alcoholate, and is conducted at temperatures between about 175.degree. F. (about 80.degree. C.) and 325.degree. F. (about 163.degree. C.), preferably at between about 210.degree. F. (about 99.degree. C.) and about 300.degree. F. (about 149.degree. C.).
U.S. Pat. No. 2,213,477 to Steindorff et al. discloses a process for producing polyglycol ethers of isocyclic hydroxyl compounds comprising reacting an alkylene glycol with a substituted isocyclic hydroxyl compound in the presence of a wide range of catalysts, including caustic alkalis, alkali alcoholates, tertiary organic bases and acid compounds (e.g. potassium bisulfate). It is noteworthy that the only example of this disclosure which employs a temperature in excess of 160.degree. C. (Example 12) utilizes powdered caustic soda (i.e., NaOH) as a catalyst.
Rowton et al., J. Org. Chem. 23 1057 (1958) discloses the reaction of phenol with 1-bromo-2,3-epoxybutane and 3-bromo-1,2-epoxybutane to yield 3-phenoxy-1,2-epoxybutane and 1-phenoxy-2,3-epoxybutane, respectively.
Parker et al., Chem Rev. 59 737 (1959) is a review article discussing mechanisms of epoxide reactions. Although reactions employing cyclohexene oxide are mentioned, no reaction parameters are cited and none of the reactions involving this compound include the reaction of cyclohexene oxide with compounds having the formula ROH, where R is phenyl or a substituted phenyl.
Posner et al., JACS 99 8208 (1977) teaches the reaction of cycloalkene oxides with alumina in which allylic alcohols are the major product. Cyclohexene oxide is specifically indicated to be unusual in that the major product of its reaction with alumina is the trans 1,2-diol. No disclosure is included of reacting these epoxides with a compound of the formula ROH.
Posner et al, JACS 99, 8214 (1977), a related article, is directed to the same subject matter as the previously recited article. This article is further removed from the instant invention in that it is directed to the reaction of three epoxides: cyclopentadiene monooxide: 1,3-cyclohexadienemonooxide: and indene oxide, which are each acid-sensitive. These compounds are reacted with alumina to produce alcoholic products similar to those produced in the above discussed article.
While certain of the above-identified processes may be employed to produce phenoxycycloalkanols, such processes frequently have drawbacks including low efficiencies and the production of undesirable sideproducts, e.g. polyethers, associated with their use.
Accordingly, it is an object of this invention to provide a process for the production of phenoxycycloalkanols, which process produces increased yields of such compounds.
It is another object of this invention to provide a process for the production of phenoxycycloalkanols, which process results in reduced amounts of undesirable byproducts, such as polyethers, being produced.
The above and additional objects will become more fully apparent from the following description and accompanying Examples.